Observations of thermal transfer OSL signals in glacigenic quartz

The conclusions of Rhodes and Pownall (Rhodes, E.J., Pownall, L., 1994. Zeroing of the OSL signal in quartz from young glaciofluvial sediments. Radiation Measurements 23, 329–333) were somewhat discouraging for the prospects of using quartz OSL for dating glacigenic sediments, while the more detailed study of Rhodes and Bailey (Rhodes, E.J., Bailey, R.M., 1997. The effect of thermal transfer on the zeroing of the luminescence of quartz from recent glaciofluvial sediments. Quaternary Science Reviews (Quaternary Geochronology) 16, 291–298) provided more encouragement. Specifically, the latter authors were able to account for the relatively high D_e values observed for recent glacigenic (dominantly glaciofluvial) sediments in terms of an anomalously high thermal transfer effect, rather than simply insufficient bleaching prior to deposition. In other locations, the OSL of quartz from glacigenic material appears to provide reliable age estimates, and does not suffer from these effects (Owen, L.A., Richards, B., Rhodes, E.J., Cunningham, W.D., Windley, B.F., Badamgarav, J., Dorjnamjaa, D., 1998. Relic permofrost structures in the Gobi of Mongolia: age and significance. Journal of Quaternary Science 13 (16), 539–548; Richards, B.W., Owen, L.A., Rhodes, E.J., 2000. Timing of Late Quaternary glaciations in the Himalayas of northern Pakistan. Journal of Quaternary Science 15, 283–297). In this paper, laboratory bleached samples from both the above studies are remeasured, using an experimental design to correct for OSL sensitivity changes, which has some similarities to the single aliquot regenerative dose (SAR) protocol of Murray and Wintle (Murray A.S., Wintle A.G., 2000. Luminescence dating of quartz using an improved single-aliquot regenerative-dose protocol. Radiation Measurements 32, 57–73). Clear evidence of thermal transfer OSL signals, generated during the preheating procedure, is presented. Further measurements, using the full SAR protocol, demonstrate that the source of this charge is related to natural dosing. For one sample, the apparent effect is subtracted effectively by the SAR protocol. Another sample studied in detail shows a striking relationship between the thermally transferred OSL signal and the total TL observed during the ramping of the preceding preheat treatment.     

Luminescence sensitivity changes of polymineral fine grains during IRSL and [post-IR] OSL measurements

Sensitivity changes during measurement sequences of infra-red-stimulated luminescence (IRSL) and post-IR optically stimulated luminescence (OSL) are presented for a sample of loess from northwestern China. Together with a dose recovery experiment, the results are used to investigate the ratio of 2.4 found for the D_e values (for IRSL and [post-IR] OSL) obtained when using a single-aliquot regenerative-dose (SAR) protocol in which both D_e values are obtained in a single sequence of measurements. Responses to test doses for both the IRSL and [post-IR] OSL show progressive luminescence sensitivity changes with repeated measurement cycles, with a slight dose dependence for the IRSL. In addition, five modified SAR procedures were used, varying preheats, filter combinations and method of measuring the luminescence signal. The D_e values for all IRSL measurements were at least 50% greater than those for the [post-IR] OSL signal. A modified SAR sequence was also applied in which 0.1 s stimulations (using both IR and blue light sources) were made between all sample treatments. A lack of consistency in the measured luminescence sensitivity of the natural IRSL signal suggests that the [post-IR] OSL signal provides the more reliable value of D_e.     

Paper II: The interpretation of measurement-time-dependent single-aliquot equivalent-dose estimates using predictions from a simple empirical model

Narrow spectrum (blue-green) laboratory partial bleaching of aliquots of natural sedimentary quartz has been shown to have a significant effect on equivalent dose (measured using a single aliquot procedure) calculated as a function of measurement time (D_e(t)). A simple model, based on empirical data, is presented in which the effects of partial bleaching on D_e(t) are predicted, taking into account the influences of pre- and post-burial doses. The model is applied to the case of heterogeneous populations of partially bleached single grains with various ranges of residual doses. Modelling shows that under realistic conditions, D_e histogram plots are unable to distinguish between samples having age overestimates and those with correct ages, whereas the proposed D_e–Z plot is able to make this distinction. Furthermore, modelling shows that D_e–Z plots can identify sub-populations of grains/aliquots that show most evidence of full bleaching, which can then be used to estimate a correct mean D_e value.     

Paper I: The use of measurement-time dependent single-aliquot equivalent-dose estimates from quartz in the identification of incomplete signal resetting

The identification of incomplete signal re-setting of optically stimulated luminescence signals in sedimentary quartz is a vitally important step in the continued improvement of optical dating. It is shown that narrow spectrum (blue-green) laboratory partial bleaching of aliquots of natural sedimentary quartz has a significant effect on equivalent dose (measured using a single aliquot procedure) calculated as a function of measurement time (D_e(t)). The blue-green stimulation spectrum mimics that found underwater and the results suggest that incomplete re-setting of waterlain sediments may be possible using the D_e(t) method.     

SnO分子的X~1∑~+,a~3Π和A~1Π态的势能曲线与光谱性质

对O原子以aug-cc-pvTZ为基组,Sn原子以aug-cc-pvTZ-PP为基组,分别采用多参考组态相互作用方法(MRCI)及运用Davidson修正的多参考组态相互作用方法对SnO分子基态X~1Σ~+及两个激发态a~3Π和A~1Π态的势能曲线进行计算,进而得到了各态的平衡键长R_e,谐振频率w_2,非谐振常数ω_ex_e,转动常数B_r,垂直跃迁能T_e以及离解能D_e,通过群论原理确定了各电子状态和离解通道,计算结果表明:3个电子态有共同的离解通道,即Sn(~3p)+O(~3p);利用Level程序对势能曲线进行拟合得到的光谱数据表明,MRCI方法的计算结果与实验值符合更好;通过求解核运动的Schrodinger方程得到了J=0时这三个电子态的前30个振动态的B_v和D_v等分子常数和振动能级E。     

75As32S+和75As34S+离子的光谱常数与分子常数

采用内收缩多参考组态相互作用(MRCI)方法, 结合Dunning系列相关一致基, 分别对⁷⁵As³²S⁺和⁷⁵As³⁴S⁺离子的X³Σ^-和A¹Π电子态的势能曲线进行了计算, 进一步拟合势能曲线, 得到各电子态的光谱常数与分子常数. 首先, 采用MRCI方法结合相关一致基, aug-cc-pV5Z, 对AsS⁺离子的X³Σ^-和A¹Π 电子态进行了计算, 获得相应的势能曲线; 然后, 为进一步提高势能曲线的精度, 对其进行了三种修正计算. 采用Davidson(+Q)方法修正MRCI 方法计算过程中存在的基组大小不一致缺陷; 利用二阶Douglas-Kroll哈密顿近似, 在cc-pVQZ基组水平, 修正了相对论效应对势能曲线的影响; 利用两点能量外推法, 在aug-cc-pVQZ和aug-cc-pV5Z基组水平对各能量点的势能值进行了外推, 得到完全基组极限处的势能曲线. 最后, 利用修正(包括Davidson修正、相对论修正和基组外推)后的势能曲线, 通过Vibrot程序, 求解双原子分子核运动的径向Schrödinger方程, 并进行同位素质量识别, 得到⁷⁵As³²S⁺和⁷⁵As³⁴S⁺离子两个电子态的光谱常数(T_e, R_e, ω_e, ω_ex_e, α_e 和B_e)和分子常数(G(ϒ), B_v, D_v).     

Luminescence dating of quartz using an improved single-aliquot regenerative-dose protocol

Single aliquot protocols are now widely used as a means of measuring the equivalent dose (D_e) in quartz and feldspar optical stimulated luminescence (OSL) dating of both heated and sedimentary materials. The most recent of these is the single-aliquot regenerative-dose (SAR) protocol, first suggested by Murray and Roberts (Radiation Measurements 29, 503–515, 1998). In this approach, each natural or regenerated dose OSL measurement is corrected for changes in sensitivity using the OSL response to a subsequent test dose (10–20% of D_e). If the sensitivity correction is adequate, then the corrected OSL response should be independent of prior dose and thermal/optical treatment, i.e. there should be no change in the sensitivity-corrected dose–response curve on remeasurement. Here we examine the interpretation of the sensitivity corrected growth curve as a function of dose, and the effect of changing measurement conditions (e.g. preheat temperature, size of test dose, stimulation temperature) on the estimation of D_e. The dependence of the dose response on prior treatment is tested explicitly, and the significance of thermal transfer discussed. It is concluded that a robust SAR protocol is now available for quartz, and that it is applicable to a wide range of heated and unheated materials.     

Circumventing possible inaccuracies of the single aliquot regeneration method for the optical dating of quartz

A simple method of assessing the reliability of the single aliquot regeneration method is presented, based on the repeated measurement of identical regeneration doses. It is shown that for the majority of the samples measured the requirement of a constant repeat point in each cycle is not met. The ability to maintain a constant repeat point is shown to be dependent upon preheating conditions, the requirements for which were found to vary at both inter-sample and inter-aliquot levels. The expected effect on estimated values of D_e is calculated and shown to be significant. Three possible means of circumventing these inaccuracies are presented: (i) adjustment of the measurement procedure (specifically the preheat conditions); (ii) modelling and correcting for the effect, and (iii) stabilising the response prior to construction of the regenerated growth curve. It is suggested that much of the variation in D_e observed between individual aliquots and between individual grains from well-bleached sediments may possibly be attributed to differences in preheating requirements, and that such differences may also account for some of the spread in D_e for partially bleached sediments.     

Internuclear potential for the B state of N2

The present method of finding the potential from spectroscopic data is tested in the irregular B state of N⁺₂. The turning points were introduced as parameters which were adjusted to give the experimental E_ν and B_ν accurately. The predicted values of r_e and D_e are quite satisfactory.     

PS自由基X2Π态的势能曲线和光谱性质

采用Davidson修正的内收缩多参考组态相互作用方法(icMRCI+Q) 结合Dunning等的相关一致基计算了PS自由基X²Π 态势能曲线. 利用三阶Douglas-Kroll Hamilton近似结合cc-pV5Z相对论收缩基进行了相对论修正计算. 利用aug-cc-pCV5Z基组对势能曲线进行了核价相关修正计算, 并将总能量外推至完全基组极限. 拟合得到了X²Π态的主要光谱常数R_e, ω_e, ω_ex_e, ω_ey_e, B_e, α_e 和D_e, 与实验结果符合较好. 利用Breit-Pauli算符, 研究了旋轨耦合效应对势能曲线的影响, 得到了两条Ω 态的势能曲线. 详细分析了在旋轨耦合计算中, 核电子相关与冻结核近似对电子结构和光谱性质的影响. 在icMRCI+Q/56+DK+CV+SO理论水平上得到了两个Ω 态的主要光谱常数T_e, R_e, ω_e, ω_ex_e, ω_ey_e, B_e 和α_e, 结果与实验结果一致. 在平衡位置处, 本文的X²Π态旋轨耦合能量分裂值为 323.73 cm^-1, 与实验结果321.93 cm^-1较为一致. 通过求解双原子分子核运动的径向Schrödinger方程, 找到了无转动PS自由基X²Π态及其两个Ω 态的全部振动态, 还分别计算了它们相应的振动能级和惯性转动常数等分子常数, 这些结果与已有的实验值一致. 关键词： 势能曲线 光谱常数 分子常数 旋轨耦合     

AlC分子 X4∑-和B4∑-电子态的光谱性质

采用Davidson修正的内收缩多参考组态相互作用方法(MRCI+Q) 结合Dunning等的相关一致基aug-cc-pVnZ (n=D,T,Q,5,6) 计算了AlC分子X⁴∑^-和B⁴∑^-态的势能曲线, 并利用总能量外推公式将这两个态的总能量分别外推至完全基组极限. 对势能曲线进行核价相关修正及相对论修正, 并详细讨论了基组、核价相关和相对论修正 等对X⁴∑^-和B⁴∑^-电子态的能量和光谱常数的影响. 拟合核价相关及相对论效应修正的外推势能曲线, 得到了AlC分子X⁴∑^- 和B⁴∑^-电子态的主要光谱常数T_e, R_e, ω_e, ω_ex_e, ω_ey_e, B_e和α_e. 它们与实验结果符合较好. 求解双原子分子核运动的径向Schrödinger方程, 找到了无转动的AlC分子两个电子态的全部振动态. 针对每一振动态, 还分别计算了其相应的振动能级和惯性转动常数等分子常数. 它们与已有的实验结果一致. 关键词： 光谱常数 分子常数 核价相关修正 相对论修正     

Simulations of the effect of pulse annealing on optically-stimulated luminescence of quartz

Pulse annealing techniques are commonly used in OSL studies of quartz to obtain information on the kinetic parameters of OSL traps and hole reservoirs. In this paper, simulations of pulse annealing experiments are carried out using the comprehensive model for quartz developed by Bailey [2001. Towards a general kinetic model for optically and thermally stimulated luminescence of quartz. Radiat. Meas. 33, 17–45] for both natural and laboratory irradiated aliquots. The results of the simulations are in qualitative agreement with, and reproduce, several unusual features of the experimental data of Wintle and Murray [1998. Towards the development of a preheat procedure for OSL dating of quartz. Radiat. Meas. 29, 81–94]. The simulations are also carried out using different heating rates, and show that pulse annealing experiments can be used to recover appropriate kinetic parameters for both the OSL traps and the hole reservoirs known to exist in quartz. The results of the simulations show the importance of these hole reservoirs in determining how the OSL signal depends upon the preheat temperature.     

Theoretical studies of spin-Hamiltonian parameters for Ni ions in CsMgX3 (X=Cl, Br, I) crystals from the two-mechanism model

In this paper, the high-order perturbation formulas of spin-Hamiltonian (SH) parameters (g factors g, g and zero-field splitting D), including both the crystal-field (CF) and for the first time charge-transfer (CT) mechanisms, are established for 3d⁸ ions in trigonal octahedral clusters. By using these formulas, the SH parameters of Ni²⁺ ions in CsMgX₃ (X=Cl, Br, I) crystals are calculated. The results are consistent with the experimental values. The calculations suggest that the sign of Q^CT (Q=Δg, Δg or D, where the g-shift Δg_i=g_i−g_e, g_e≈2.0023 is the value of free-electron) due to CT mechanism is the same as that of the corresponding Q^CF due to CF mechanism, and the relative importance of CT mechanism (characterized by Q^CT/Q^CF) increases with the increasing atomic number of ligand X. So, for the 3dⁿ ML_m clusters with ligand having large atomic number, the reasonable theoretical explanations of all SH parameters should take both CF and CT mechanisms into account. The defect structure of (NiX₆)⁴⁻ impurity centers in CsMgX₃:Ni²⁺ crystals is also considered in our model.     

Binding energy of the donor impurities in GaAs-Ga_(1-x)Al_xAs quantum well wires with Morse potential in the presence of electric and magnetic fields

The behavior of a donor in the GaAs–Ga_(1-x)Al_xAs quantum well wire represented by the Morse potential is examined within the framework of the effective-mass approximation. The donor binding energies are numerically calculated for with and without the electric and magnetic fields in order to show their influence on the binding energies. Moreover, how the donor binding energies change for the constant potential parameters(De, re, and a) as well as with the different values of the electric and magnetic field strengths is determined. It is found that the donor binding energy is highly dependent on the external electric and magnetic fields as well as parameters of the Morse potential.     

SN-分子离子的势能函数和光谱常数研究

采用耦合簇CCSD(T)方法结合系列相关一致基组aug-cc-pVXZ (X=D,T,Q,5) 对基态SN^-分子离子(X³∑^-) 进行了结构优化和单点能扫描计算. 用四种方法进行基组外推得到该体系的平衡核间距R_e=0.15852 nm, 谐振频率ω_e=948.05 cm^-1, 离解能D_e=3.934 eV均与实验数据符合得很好. 对单点能扫描结果用9参数Murrell-Sorbie势能函数进行了最小二乘拟合, 得到了体系的解析势能函数表达式, 并进一步推导出了体系的力常数和光谱常数. 拟合所得势能曲线准确地再现了SN^-分子离子的离解能和平衡结构特征. 通过求解核运动的径向薛定谔方程, 得到了无转动SN^- (X³∑^-) 的全部振动态, 并进一步计算出了各振动能级相应的分子常数. 与实验结果及其他理论研究结果的对比表明, 本文关于SN^-分子离子平衡常数和光谱常数的计算结果达到了较高的精度, 能为进一步的实验探测和理论研究提供参考依据. 关键词： 势能曲线 解析势能函数 光谱常数 振动能级     

Investigations of the performance of quartz single aliquot DE determination procedures

Over the past few years a variety of equivalent dose (D_E) determination techniques for quartz, which are truly single aliquot-based, have been proposed. Such methods avoid the need for inter-aliquot normalisation, and provide considerable improvements in the precision of equivalent dose (D_E) estimates. Much of the research leading to these developments have been based on detailed investigations of a few samples, primarily from Australia. All ’protocols’ developed have performed impressively. It is necessary, however, to verify the consistency of the single aliquot D_E determination methods on a wide range of samples before they can be considered as prescribed or standard. We have analysed approximately 100 samples from a range of sedimentary environments and geological provinces in an attempt to confirm the robustness of the single aliquot techniques. Up to 65% of samples measured in our laboratory were not suited to analysis via application of single aliquot additive dose (SAAD) procedures. This relates to a range of factors, including lack of sample sensitivity and dose dependent sensitivity changes. Furthermore, we have observed some problems in dating young sediments using single aliquot regeneration (SAR) methods. Critically, we observe that sample to sample variability on quartz luminescence (thermally- and optically-stimulated) behaviour is considerable, and many samples are found to exhibit behaviour which contrasts greatly from that described in recent phenomenological studies.     

LiAl分子基态、激发态势能曲线和振动能级

利用单双激发多参考组态相互作用方法获得了LiAl分子基态X¹∑⁺及七个激发态a³∏, A¹∏, b³∑⁺, c³∑⁺, B¹∏, C¹∑⁺, d³∏的势能曲线, 通过势能曲线得到各态的平衡核间距R_e, 进而求得绝热激发能和垂直激发能.计算结果表明:c³∑⁺ 电子态是一个不稳定的排斥态, A¹∏态是一个较弱的束缚态, 其余6个电子态均为束缚态; b³∑⁺与 c³∑⁺态之间存在预解离现象; 8个电子态分别解离到两个通道, 即Li(²S)+Al(²P⁰)与Li(²P⁰)+Al(²P⁰). 接着将势能曲线拟合到Murrel-Sorbie解析势能函数形式, 据此获得各态的光谱数据:基态X¹∑⁺的平衡键长为0.2863 nm, 谐振频率为316 cm^-1, 解离能D_e为1.03 eV, 激发态a³∏, A¹∏, b³∑⁺, c³∑⁺, B¹∏, C¹∑⁺, d³∏的垂直激发能依次为0.27, 0.83, 1.18, 1.14, 1.62, 1.81, 2.00 eV; 解离能依次为1.03, 0.82, 0.26, 排斥态, 1.54, 1.10, 0.93 eV, 相应谐振频率 ω_e为339, 237, 394, 排斥态, 429, 192, 178 cm^-1. 通过求解核运动的薛定谔方程找到了J=0时 LiAl分子7个束缚电子态的振动能级和转动惯量. 关键词： LiAl 光谱常数 势能曲线 振动能级     

Na_2~+离子较低电子态势能曲线和光谱常数的理论研究

通过多组态相互作用方法,结合原子有效芯势与极化势,利用非收缩的高斯基函数,计算了Na_2~+分子对应最低9个解离限的36个电子态的势能曲线.基于计算获得的束缚态势能曲线,拟合给出了相应的光谱常数,并与已有的实验和理论结果进行了比较.同时,给出了部分电子态的振动-转动能级和一些同类态避免交叉点的信息.计算获得的光谱信息对冷原子分子光谱与动力学的研究具有参考价值.     

Study of the 110°C TL peak sensitivity in optical dating of quartz

As the 110°C TL emission in quartz uses the same luminescence centers as the OSL emission, the 110°C TL signal from a test dose may be used to monitor the OSL sensitivity change. It is thus important to study the relationship between the 110°C TL peak and the OSL sensitivity in studies related to optical dating from quartz. We have conducted a series of experiments using sedimentary quartz, where the annealing temperatures were varied between 260 and 1000°C before the measurement of OSL and 110°C TL sensitivities. Another series of experiments on two sedimentary quartz samples investigated the 110°C TL peak and OSL dose-dependent sensitivity change after different annealing temperatures. In these experiments, the 110°C TL and OSL signals from the test dose are shown to have similar sensitization characteristics: the 110°C TL sensitivity change is proportional to the OSL sensitivity change if the annealing temperature is lower than 500°C. It is concluded that the 110°C TL signal can be used to correct the OSL sensitivity change in the single-aliquot additive-dose protocol.     

Optically stimulated luminescence production in the single-aliquot regenerative dose protocol

When using a single-aliquot regenerative dose (SAR) protocol for luminescence dating of sedimentary quartz grains, the fundamental assumption is that the sensitivity of the optically stimulated luminescence (OSL) produced by the regenerative doses can be monitored by their following test dose OSL response. Using well-bleached coarse quartz grains, OSL production in a SAR protocol was studied in detail when dose response curves were constructed using both single and multiple aliquot regenerative dose procedures. During application of the SAR protocol, two preheats are applied, each ahead of an OSL measurement that is produced by the regenerative dose and test dose, respectively. It is shown that sensitivity changes caused by heating were well corrected for using the OSL response to the test dose. However, these preheats are shown to result in thermally stimulated OSL signals that contribute both to the OSL response from the regenerative doses used to construct the dose response curve and to the OSL response from the test dose used to monitor OSL sensitivity changes as the quartz grains are repeatedly measured. A simple test is proposed to identify the contribution of the latter signal.